CN101300303A - Poly(arylene ether) blend and method of making same - Google Patents

Poly(arylene ether) blend and method of making same Download PDF

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CN101300303A
CN101300303A CNA2006800408917A CN200680040891A CN101300303A CN 101300303 A CN101300303 A CN 101300303A CN A2006800408917 A CNA2006800408917 A CN A2006800408917A CN 200680040891 A CN200680040891 A CN 200680040891A CN 101300303 A CN101300303 A CN 101300303A
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poly
composition
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alkenyl aromatic
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迈克尔·L·托特
杰弗里·H·赖丁
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SHPP Global Technologies BV
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A resin composition includes a poly(arylene ether), a poly(alkenyl aromatic) having a melt index of about 10 to about 250 grams/minute as measured by ASTM D 1238, Procedure B at 200 DEG C. and 5 kilogram load, and a rubber-modified poly(alkenyl aromatic). The composition exhibits improved flow in extrusion and molding operations.

Description

Poly (arylene ether) blend and manufacture method thereof
Background of invention
The present invention relates to poly (arylene ether) composition, relate more specifically to the high workability poly (arylene ether) composition.
The polyarylene ether resin is as polyphenylene oxide (PPE) resin, because their stability to hydrolysis, high-dimensional stability, toughness, thermotolerance and dielectric properties are exceedingly useful class high-performance engineering thermoplasticss.It is well known in the art that this not the unique combination of performance of the same race cause the poly (arylene ether) based composition to be applicable to the application of broad range.For example, poly (arylene ether) blend is widely used in fields such as trolley part, electrical component, office equipment.
The aspect that poly (arylene ether) composition need improve is a melt flowability, that is, the various process segments as extrude with molding in when temperature raises free-pouring ability.Bad melt flow can influence the size and the type of the parts that can be made by said composition.
Therefore, exist the lasting demand of the flowability of improving poly (arylene ether) composition in the art.
The invention summary
Satisfied the demand by the resin combination that contains following material: poly (arylene ether); Poly-(alkenyl aromatic), it is according to ASTM D 1238, and the melt index that rules B records when the load of 200 ℃ and 5 kilograms is about 10 to about 250 gram/minute; Poly-(alkenyl aromatic) with modified rubber.
The present invention also provides the method for preparing said composition.
Detailed Description Of The Invention
In this specification sheets and claims, with reference to being defined as a plurality of terms with following meanings.
Singulative " one (a) ", " one (an) " and " being somebody's turn to do (the) " comprise plural indicator, unless context is clearly pointed out in addition.
" optional " or " randomly " means: described subsequently incident or situation can or can not take place, and this specification sheets comprises situation that this incident wherein takes place and its situation that does not take place wherein.
" combination " used herein comprises mixture, multipolymer, reaction product, blend, matrix material or the like.
And the end points of the four corner of narration same characteristic features is combinative independently and comprises described end points.
Find: compare with the blend of poly-(alkenyl aromatic) that only contain poly (arylene ether) and modified rubber, comprise a) poly (arylene ether), b beyond expectationly) poly-(alkenyl aromatic) of high workability and c) blend of poly-(alkenyl aromatic) of modified rubber have the enhanced melt flow.Below will be described more specifically it.
The melt index of poly (arylene ether) blend is more than or equal to about 20 gram/minute, particularly more than or equal to 25 gram/minute, even more specifically more than or equal to 30 gram/minute, wherein melt index is according to the D 1238 of U.S. test material association (" ASTM "), and rules B records when the load of 280 ℃ and 5 kilograms.And in one embodiment, the melt index of poly (arylene ether) blend is 20 gram/minute to 200 gram/minute, more specifically 25 gram/minute to 100 gram/minute.
As used herein, poly (arylene ether) comprises the structural unit of a plurality of general formulas (I):
Figure A20068004089100051
In the formula for each structural unit, each Q 1Be the halo-oxyl that halogen, uncle or secondary low alkyl group (for example, containing 1 alkyl to about 7 carbon atoms), phenyl, haloalkyl, aminoalkyl group, thiazolinyl alkyl, alkynyl alkyl,-oxyl, aryl and at least 2 carbon atoms separate halogen and Sauerstoffatom independently; And each Q 2Be the halo-oxyl that hydrogen, halogen, uncle or secondary low alkyl group (for example, containing 1 alkyl to about 7 carbon atoms), phenyl, haloalkyl, aminoalkyl group, thiazolinyl alkyl, alkynyl alkyl,-oxyl, aryl and at least 2 carbon atoms separate halogen and Sauerstoffatom independently.In some embodiments, each Q 1Be C independently 1-C 4Alkyl or phenyl, and each Q 2Be hydrogen or methyl independently.Poly (arylene ether) can comprise the molecule with the end group that contains aminoalkyl group, and described end group is usually located at the ortho position of hydroxyl.Also usually there is tetramethyl diphenoquinone (TMDQ) end group, usually by obtaining in the reaction mixture that has the tetramethyl diphenoquinone by product.
The form of poly (arylene ether) can be homopolymer, multipolymer, graft copolymer, ionomer or segmented copolymer and comprise aforementioned at least a combination.For example, in one embodiment, poly (arylene ether) comprises and contains 2,6-dimethyl-1, and the 4-phenylene ether units is randomly with 2,3,6-trimethylammonium-1, the polyphenylene oxide of the combination of 4-phenylene ether units (PPE).
Poly (arylene ether) can pass through monohydroxy aromatics such as 2 and 2,3, the oxidative coupling of 6-pseudocuminol and preparing.Usually the catalyst system that is used for this class coupling; They can comprise heavy metal compound such as copper, manganese or cobalt compound, and usually combination has various other materials such as secondary amine, tertiary amine, N, N '-dialkyl group Alkylenediamine, halogenide or aforesaid both or more combination.
Available polyfunctional compound (contain simultaneously (a) carbon-to-carbon double bond or carbon-to-carbon triple bond and (b) those compounds of at least one carboxylic acid, acid anhydrides, acid amides, ester, imide, amino, epoxy, ortho ester or hydroxyl) functionalized poly arylene ether as poly carboxylic acid or in molecule.
This type of polyfunctional compound's example comprises toxilic acid, maleic anhydride, FUMARIC ACID TECH GRADE and citric acid.
Poly (arylene ether) can have about 3,000 gram every mole (g/mol) is to about 40, the number-average molecular weight of 000g/mol and about 5,000g/mol is to about 80, the weight-average molecular weight of 000g/mol, in 40 ℃ the time, the sample that uses monodispersed polystyrene standards (SDEB styrene diethylenebenzene gel) and have 1 milligram of every milliliter of chloroform is measured by gel permeation chromatography for it.Record in 25 ℃ of chloroforms, the combination of poly (arylene ether) or multiple poly (arylene ether) has the initial intrinsic viscosity of 0.3 deciliter of every gram (dl/g) to 0.6 deciliter of every gram (dl/g).Initial intrinsic viscosity is defined as the limiting viscosity of poly (arylene ether) before mixing with other component melts in the composition.Be that the viscosity of poly (arylene ether) can raise 30% for known to a person of ordinary skill in the art after melting mixing.The per-cent that increases can calculate by (final response viscosity-initial intrinsic viscosity)/initial intrinsic viscosity.When using two initial intrinsic viscosity, accurately the definite of ratio will be depended on the accurate limiting viscosity of used poly (arylene ether) and desired final physical character to a certain extent.
The consumption of poly (arylene ether) is generally 10 weight percents (weight %) to 99.5 weight %.In this scope, the consumption of poly (arylene ether) can be more than or equal to 20 weight %, and more particularly more than or equal to 30 weight %.In this scope that coexists, the consumption of poly (arylene ether) can be to be less than or equal to 85 weight %, and more particularly is less than or equal to 80 weight %.Weight percent is based on the gross weight of said composition.
Said composition also comprises poly-(alkenyl aromatic) of high workability.About the term high workability of poly-(alkenyl aromatic) component be meant have 10 grams per minutes (" g/min ") to poly-(alkenyl aromatic) of the melt index of 250 grams per minutes, wherein melt index is by ASTM D 1238, and rules B records when the load of 200 ℃ and 5 kilograms.In one embodiment, this melt index is more than or equal to 20 gram/minute, in addition more specifically this melt index more than or equal to 30 gram/minute.
Particularly, said composition comprises the monomeric homopolymer of alkenyl aromatic, and wherein the alkenyl aromatic monomer has general formula (II):
Figure A20068004089100071
R in the formula 1Be hydrogen, low alkyl group or halogen; Z 1Be vinyl, halogen or low alkyl group; And p is 0,1,2,3,4 or 5.Concrete alkenyl aromatic monomer comprises vinylbenzene, chloro-styrene and Vinyl toluene.The monomeric homopolymer of alkenyl aromatic is to be derived from cinnamic homopolymer (being homopolystyrene) more specifically.In one embodiment, at least 99% of homopolystyrene weight 100% of its weight is derived from vinylbenzene particularly.
Based on the gross weight of said composition, the amount of the alkenyl aromatic monomer homopolymer that said composition can contain is extremely about 20 weight % of about 5 weight %, and about especially 7.5 weight % are to about 16 weight %.
In one embodiment, poly-(alkenyl aromatic) of high workability is substantially free of mineral oil.Term is substantially free of the gross weight that is meant based on poly-(alkenyl aromatic) of high workability, and poly-(alkenyl aromatic) of high workability comprises and be less than about 0.1 weight % mineral oil.In this embodiment, poly-(alkenyl aromatic) of high workability do not contain the mineral oil of having a mind to adding especially.
In one embodiment, poly-(alkenyl aromatic) of high workability comprises the general purpose polystyrene (GPPS) of high workability.And high workability GPPS does not generally obtain as former green material (virgin material), and it easily obtains as polystyrene foamed (EPS) wrapping material that reclaim.
The normally about 5 weight % of consumption of poly-(alkenyl aromatic) of high workability are to about 20 weight %.In this scope, poly-(alkenyl aromatic) of high workability can be more than or equal to about 7.5 weight %, and more particularly more than or equal to about 8.5 weight %.In this scope, poly-(alkenyl aromatic) of high workability can be to be less than or equal to about 16.5 weight %, and more particularly is less than or equal to about 15 weight % equally.Weight percent is based on the gross weight of said composition.
Said composition also comprises poly-(alkenyl aromatic) resin of modified rubber.Poly-(alkenyl aromatic) resin of modified rubber comprises and is derived from least a above-mentioned alkenyl aromatic polymer of monomers, and also is included as the rubber modifier of blend and/or grafted form.This rubber modifier can be at least a C 4-C 10The polymerisate of non-aromatics diene monomers (as divinyl or isoprene).Poly-(alkenyl aromatic) resin of this modified rubber comprises the rubber modifier of about 98 weight % to poly-(alkenyl aromatic) resin of about 70 weight % and about 2 weight % to about 30 weight %, the rubber modifier of about particularly 94 weight % to poly-(alkenyl aromatic) resin of about 88 weight % and about 6 weight % to about 12 weight %.
Poly-(alkenyl aromatic) resin of concrete modified rubber comprises and contains the styrene-butadiene copolymer of 88 weight % to the vinylbenzene of about 94 weight % and about 6 weight % to the divinyl of about 12 weight % of having an appointment.These styrene-butadiene copolymers are also referred to as high-impact polystyrene (HIPS), are commercially available, for example as originating from the GEH 1897 of General Electric Company and originating from the BA 5350 of Chevron Chemical Company.
The consumption of poly-(alkenyl aromatic) of this modified rubber is generally about 10wt.% to about 70 weight %.In this scope, poly-(alkenyl aromatic) of this modified rubber can be more than or equal to about 20 weight %, and more particularly more than or equal to about 30 weight %.In this scope that coexists, poly-(alkenyl aromatic) of this modified rubber can be to be less than or equal to about 65 weight %, and more particularly is less than or equal to about 60 weight %.Weight percent is based on the gross weight of said composition.
In one embodiment, poly-(arylene ether) is by the amount existence of about 20 weight % to about 80 weight %; Poly-(alkenyl aromatic) is by the amount existence of about 5 weight % to about 20 weight %; And poly-(alkenyl aromatic) of modified rubber is by the amount existence of about 10 weight % to about 70 weight %; Wherein wt per-cent is based on the gross weight of said composition.
Said composition also can comprise at least a fire retardant, and it is generally halogenated materials, organophosphate or both combinations.
In one embodiment, said composition comprises organic phosphate flame retardant, and wherein organophosphate is the aromatic phosphoric acid ester compound with general formula (III):
Figure A20068004089100081
R is identical or different in the formula, and is alkyl, halogen or aforementioned arbitrary combination that aryl, halogenated aryl, aryl that alkyl, cycloalkyl, aryl, alkyl replace replace, and prerequisite is that at least one R is an aryl.
Example comprises phosphoric acid phenyl two (dodecyl) ester, phosphoric acid phenyl two (neo-pentyl) ester, phosphoric acid phenyl two (3,5,5 '-the trimethylammonium hexyl) ester, phosphoric acid ethyl diphenyl, phosphoric acid 2-ethylhexyl two (right-tolyl) ester, di(2-ethylhexyl)phosphate (2-ethylhexyl) is right-the tolyl ester, lindol, di(2-ethylhexyl)phosphate (2-ethylhexyl) phenylester, tricresyl phosphate (nonyl phenyl) ester, di(2-ethylhexyl)phosphate (dodecyl) is right-the tolyl ester, Tritolyl Phosphate, triphenylphosphate, di(2-ethylhexyl)phosphate butyl phenyl ester, phosphoric acid 2-chloroethyl diphenyl, phosphoric acid is right-tolyl two (2,5,5 '-the trimethylammonium hexyl) ester, phosphoric acid 2-ethylhexyl diphenyl, or the like with their combination.In one embodiment, phosphoric acid ester is the phosphoric acid ester that each R is the aryl of aryl or alkyl replacement.
Perhaps, organophosphate can be to have following formula (IV), (V) or two-or many-functional compound or polymkeric substance (VI), comprises their mixture.
Figure A20068004089100091
Figure A20068004089100101
R wherein 1, R 3With R 5Be alkyl independently; R 2, R 4, R 6With R 7Be alkyl or-oxyl independently; X 1, X 2With X 3Be halogen; M and r are 0,1,2,3 or 4 independently; And n and p are 1 to about 30 integer independently.
Example comprises and is respectively Resorcinol, quinhydrones and two (phenylbenzene) bisphenol-A phosphoric acid ester, and their polymeric counterpart (counterpart).
Prepare above-mentioned two-or the method for many-functional aromatic phosphate acid ester be described in English Patent No.2,043,083.
The useful organic fire-retardant of another group comprises some annular phosphate (cyclic phosphates), for example, diphenyl pentaerythritol bisphosphate (diphenyl pentaerythritol diphosphate), fire retardant as poly-(arylene ether) resin is described in U.S. Patent No. 4 by Axelrod, 154,775.
Useful especially organophosphate comprises the phosphoric acid ester of the phenyl that contains replacement, based on the phosphoric acid ester of Resorcinol such as, for example, bisphosphate Resorcinol tetraphenyl ester, and based on the phosphoric acid ester of bis-phenol, for example, bisphosphate bisphenol-A tetraphenyl ester.In one embodiment, organophosphate is selected from triphenylphosphate and above-mentioned both or the more mixture of butylated triphenylphosphate, resorcinol diphosphate (resorcinol diphosphate), bisphosphate bisphenol-A ester, triphenylphosphate, isopropylation.
In various embodiments, said composition also can comprise at least a additive such as antioxidant, dripping inhibitor, dyestuff, pigment, tinting material, stablizer, mineral particles filler (such as clay, mica and talcum), static inhibitor, softening agent, slipping agent, the glass fibre (long, cut-out or pulverizing) of significant quantity and contain aforementioned at least a kind of combination.These additives are well known in the art, and their level of significance and blending means also are like this.The significant quantity of each additive differs greatly, but they exist by about 60 weight % of as many as or more total amount in the gross weight of said composition.Common gross weight in said composition, additive such as antioxidant, fire retardant, dripping inhibitor, dyestuff, pigment, tinting material, stablizer, static inhibitor, softening agent, slipping agent etc. exist to the amount of about 5 weight % by about 0.01 weight %, and mineral particles filler and glass fibre account for about 1 weight % of gross weight of said composition to about 60 weight %.
Can prepare said composition by melting mixing or dry blending and melting mixing combination.Melting mixing can single-or two-screw extrusion press maybe can impose in the similar mixing device of shearing and carry out component.
All the components can begin to add to treatment system.In some embodiments, poly-(arylene ether) can with the expanding material pre-mixing to form functionalized poly-(arylene ether).Functionalized poly-(arylene ether) mixes with other component again.In another embodiment, mix poly-(arylene ether), expanding material and optional additive to form first material, poly-(alkenyl aromatic) of remix high workability and poly-(alkenyl aromatic) and first material of modified rubber.
In various other embodiments, when using forcing machine, can add all or part of of the gathering of poly-(alkenyl aromatic) of high workability and modified rubber (alkenyl aromatic) in fusion poly-(arylene ether) back, for example, add by downstream port.When work in-process uses isolating forcing machine, be prepared in the single forcing machine of supplying various components and simplified processing having a plurality of opening for feeds along its length direction.By the one or more venting ports in the forcing machine melts is imposed vacuum and help removing volatile impunty in the said composition often.
In one embodiment, said composition comprises poly-(alkenyl aromatic) of poly-(arylene ether), high workability and the reaction product of gathering (alkenyl aromatic) of modified rubber.The aforementioned component that is defined as by two or more of " reaction product " of Shi Yonging is being used to form the product that (for example, in melting mixing or high shear mixing) under the condition of composition reaction produces herein.
After forming composition, be generally shaped to the line material, its cutting is to form pellet.Usually selection wire material diameter and pellet length are to stop or to reduce the top efficiency that produces fines (volume is less than or equal to the particulate of pellet 50%) and extrude for following process such as section bar.The length of exemplary pellet is about 1 millimeter (mm) to about 5mm and the diameter of exemplary pellet is about 1mm about 5mm extremely.
Said composition can by low shear thermoplastic processing as film and sheet material extrude, profile is extruded, extrusion molding, compression moulding and blowing are converted into goods.Film and sheet material extrude that processing can comprise and be not limited to the fusion curtain coating, blown film is extruded and roll (calendaring).Can use coextrusion and lamination process to form composite multilayer membrane or sheet.Also can impose list or laminated coating to give additional properties such as anti-scratch, ultraviolet light, aesthetic feeling or the like to list or multiwalled substrate.Coating can be used by standard application techniques such as roller coat, spraying, dipping, brushing or flow coat.
Oriented film can use conventional stretching technique to extrude or prepare by stretching curtain coating or calendered film through blown film near heat-drawn wire.For example, the radial drawing pantograph can be used for multiaxis and stretches simultaneously; X-y direction stretching pantograph is used in plane x-y direction and stretches simultaneously or sequentially.Also can use to have the coaxial single shaft of order and stretch to obtain single shaft and biaxial stretch, for example be equipped with and be used for tensile differential velocity roller (differential speed roll) and be equipped with partly and at horizontal direction and be used for the stretch tight machine of frame part (tenter frame section) of tensile tentering at longitudinal direction to the equipment of elongation stretched portion.
Said composition can be converted into multilayer tablet, it comprises second that has first and second first and have first and second, wherein first comprises thermoplastic polymer, and wherein first first face places first of a plurality of timbers (ribs); Wherein second comprises thermoplastic polymer, and wherein second first face places second of a plurality of timbers, and wherein first of a plurality of timbers with a plurality of timbers second is opposite.
Above-mentioned film and sheet material can also be processed as moulded products by thermoplastic by moulding and molding methods, and this moulding and molding methods include but not limited to thermoforming, vacuum forming, pressing pressure moulding, injection moulding and compression moulding.Multilayer formed article can also form by thermoplastic resin being injection-moulded in single or multiple lift film as described below or the sheet substrate:
Be provided at the surface and have and choose any one kind of them or the single or multiple lift thermoplastic substrate of multiple color, for example, use the silk screen printing of dye transfer (transfer dye), make substrate consistent with mould structure.
For example by with the substrate moulding and be cut into 3D shape and this substrate is enclosed in the mould, this mould has the surface that the 3D shape with substrate is complementary.
The mold cavity that thermoplastic resin is injected base substrate rear surface makes substrate consistent with mould structure, so that (i) the preparation permanent bonded three-dimensional objects of monoblock or (ii) pattern or aesthetic effect are transferred to the resin of injection and remove printing substrate from printing substrate is given the moulding resin aesthetic effect thus.
Those skilled in the art also will recognize, common curing and surface modifying method include but not limited to thermofixation, veining (texturing), embossing, corona treatment, flame treating (flame treatment), Cement Composite Treated by Plasma and vacuum moulding machine, can further be applied to said products, to change appearance and to give goods extra function.
Therefore, another embodiment relates to goods, sheet and the film by top preparation of compositions.
Typical goods comprise all or part of of following goods:
Furniture, dividing plate (partitions), container, the car inner part (comprises railcar, railcar, bus, electric car, aircraft, motor vehicle and recreational vehicle), outboard component such as push rod, utensil (appliances), cooker, electrical equipment, Analytical equipment, window frame, wire conduit, the floor, baby's furniture and equipment, telecommunication equipment, the antistatic packaging of electronics and parts, health care goods such as hospital bed and dentist's chair, sports equipment, generator shell, display casing, business appliance parts and shell, lamp housing, mark, air-treating unit and shell, automobile cover lower member.
Following non-limiting examples is further illustrated various embodiments described herein.
Embodiment
Embodiment uses the material of listing in the table 1.The amount of using among the embodiment is the weight percent by composition total weight, except as otherwise noted.
Table 1
Material Illustrate/supplier
PPE Poly-(2,6-dimethyl-1,4-phenylene ether) record the limiting viscosity of 0.46dl/g in 25 ℃ of chloroforms, GE Advanced Materials is on sale
High workability HIPS 7.7 melt flow index, 8.4% rubber originates from the 876HF of Japan Polystyrene
Standard HIPS 2.7 melt flow index, 10.3% rubber originates from the HIPS3190 of GE
High workability GPPS 69.4 melt flow index, do not have commercially availablely, sample is provided by University of Kentucky
Fire retardant Originate from the resorcinol diphosphate (RDP) of Supresta
Styrene-acrylonitrile is sealed tetrafluoroethylene GE Plastics
LLDPE Nova Chemicals Novapol GM-2024A
Tricresyl phosphate (2,4-two-tert-butyl phenyl) ester Ciba Specialty Chemicals
Tridecyl phosphite Crompton，TDP Weston
Zinc sulphide Sachtleben，SACHOLITH HD ZNS
Magnesium oxide Western Reserve，MagChem HAS-10
Zinc oxide GH Chemical Company，CR-4
Embodiment 1-4 finishes by mix each component in twin screw extruder.Extruded material is injection molded into the sample that is used for the physical properties test.Physical properties, unit and their testing method are listed in the table 2.Megapascal (MPa) is abbreviated as MPa, and joule is abbreviated as J, and rice is abbreviated as m, and grams per minute is abbreviated as g/min.Composition and the data of embodiment are listed in the table 3.
Table 2
Physical properties Unit Testing method
Tensile yield strength MPa ASTM D638
The tensile fracture elongation rate ％ ASTM D638
Tensile modulus MPa ASTM D638
1/8 " deflection yielding stress MPa ASTM D790
1/8 " modulus in flexure MPa ASTM D790
23 ℃ of notched izod are impacted J/m ASTM D256
1/4 " Re Bianxingwendu @1.8MPa ℃ ASTM D648
Rong Tizhishuo @280 ℃/5kg g/min ASTM D1238
Table 3
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
PPE 34.25 34.25 47.63 47.63
High workability HIPS 63.74 0 33.93 0
Standard HIPS 0 47.81 0 25.45
High workability GPPS 0 15.94 0 8.48
Fire retardant 0 0 16.39 16.39
Styrene-acrylonitrile is sealed tetrafluoroethylene 0 0 0.49 0.49
LLDPE 1.46 1.46 1.22 1.22
Tricresyl phosphate (2,4-two-tert-butyl-phenyl) ester 0 0 0.08 0.08
Tridecyl phosphite 0.48 0.48 0 0
Zinc sulphide 0.1 0.1 0.12 0.12
Magnesium oxide 0 0 0.12 0.12
Zinc oxide 0.1 0.1 0 0
Tensile yield strength 53.6 51.2 65.6 64.5
The tensile fracture elongation rate 20.9 23.7 9.11 9.66
Tensile modulus 2840 2750 2620 2610
1/8 " deflection yielding stress 88.4 84.4 103 102
1/8 " modulus in flexure 2600 2630 2820 2850
23 ℃ of notched izod are impacted 156 174 177 157
1/4 " Re Bianxingwendu @1.8MPa 110 111 98.1 93.4
Rong Tizhishuo @280 ℃/5kg 33.8 64.3 32.1 31.3
As can be seen from Table 3, the use of high workability GPPS causes composition to have melt flow index more than or equal to about 31 gram/minute.In embodiment 2, melt flow index is 64.3 gram/minute, and it has significant raising with respect to the embodiment 1 that uses high workability HIPS.In embodiment 1, melt flow index is 33.8 gram/minute.And the mechanical property with composition (embodiment 2 and embodiment 4) of high workability GPPS is substantially equal to or is better than not using the composition of high workability GPPS.
Advantageously, use high workability GPPS to reduce or avoid using high workability HIPS used in the said composition.Because the cost of high workability GPPS significantly is lower than the cost of standard HIPS and high workability HIPS, can realize the reduction of production cost.The improvement that the reduction of these costs adds with respect to the composition that contains high workability HIPS shows significant commercial advantage.
Though reference example embodiment and described the present invention one skilled in the art will understand that not departing from and can carry out various variations under the scope of the present invention, and can replace its key element with equivalent.In addition, do not depart under its base region, can carry out many improvement to be applicable to concrete occasion or material according to of the present invention being taught in.Therefore, it means the present invention and is not limited to as being contemplated to and implements best mode of the present invention and disclosed embodiment, will comprise all embodiments in the scope that falls into appended claims but mean the present invention.

Claims (20)

1. resin combination comprises:
Poly (arylene ether);
Poly-(alkenyl aromatic), it is according to ASTM D 1238, and the melt index that rules B records when the load of 200 ℃ and 5 kilograms is extremely about 250 gram/minute of about 10 gram/minute; With
Poly-(alkenyl aromatic) of modified rubber.
2. the composition of claim 1, the melt index of wherein said poly-(alkenyl aromatic) is more than or equal to about 30 gram/minute.
3. the composition of claim 1, wherein said poly (arylene ether) exists to the amount of about 80 weight % by about 20 weight %; Described poly-(alkenyl aromatic) is by the amount existence of about 5 weight % to about 20 weight %; And poly-(alkenyl aromatic) of described modified rubber is by the amount existence of about 10 weight % to about 70 weight %; Wherein wt per-cent is based on the gross weight of said composition.
4. the composition of claim 1, wherein according to ASTM D 1238, rules B records said composition and has the composition melt index of about 20 gram/minute to about 200 gram/minute when the load of 280 ℃ and 5 kilograms.
5. the composition of claim 4, wherein said composition melt index is more than or equal to about 30 gram/minute.
6. the composition of claim 1, wherein the initial intrinsic viscosity that records in 25 ℃ of chloroforms of this poly (arylene ether) is that about 0.3 deciliter of every gram is to about 0.6 deciliter of every gram.
7. the composition of claim 1, wherein said poly-(alkenyl aromatic) is substantially devoid of mineral oil.
8. the composition of claim 1, wherein said poly (arylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units.
9. the composition of claim 1, wherein said composition also comprises organic phosphate flame retardant.
10. the composition of claim 9, wherein said organophosphorus ester flame-proof agent comprises resorcinol diphosphate.
11. the composition of claim 1, poly-(alkenyl aromatic) of wherein said modified rubber comprise the styrene butadiene graft copolymer of the polyhutadiene of the polystyrene that contains 88 weight % to the 94 weight % that have an appointment and about 6 to 12 weight %.
12. comprise the goods of the composition of claim 1.
13. a resin combination comprises:
Poly (arylene ether), it records initial intrinsic viscosity in 25 ℃ of chloroforms be about 0.3 to about 0.6 deciliter of every gram;
Poly-(alkenyl aromatic), it is according to ASTM D 1238, and the melt index that rules B records when the load of 200 ℃ and 5 kilograms is extremely about 250 gram/minute of about 10 gram/minute; With
Poly-(alkenyl aromatic) of modified rubber, comprise containing the styrene butadiene graft copolymer of 88 weight % of having an appointment, by the gross weight of gathering (alkenyl aromatic) of modified rubber to the polystyrene of about 94 weight % and about 6 weight % to the polyhutadiene of about 12 weight %.
14. the composition of claim 13, wherein said melt index is more than or equal to about 30 gram/minute.
15. the composition of claim 13, wherein said poly (arylene ether) is by the amount existence of about 20 weight % to about 80 weight %; Described poly-(alkenyl aromatic) is by the amount existence of about 5 weight % to about 20 weight %; And poly-(alkenyl aromatic) of described modified rubber is by the amount existence of about 10 weight % to about 70 weight %; Wherein wt per-cent is based on the gross weight of said composition.
16. the composition of claim 13, wherein according to ASTM D 1238, the composition melt index of the said composition that rules B records when the load of 280 ℃ and 5 kilograms is that about 20 gram/minute are to about 200 gram/minute.
17. the composition of claim 16, wherein the said composition melt index is more than or equal to about 30 gram/minute.
18. make the method for resin combination, it comprises:
The melting mixing poly (arylene ether) is to form first melts; And
Melting mixing
Poly-(alkenyl aromatic), according to ASTM D 1238, the melt index that rules B records when the load of 200 ℃ and 5 kilograms is extremely about 250 gram/minute of about 10 gram/minute,
Poly-(alkenyl aromatic) of modified rubber and
Described first melts.
19. the method for claim 18, the melt index of wherein said poly-(alkenyl aromatic) is more than or equal to about 30 gram/minute.
20. the method for claim 18, wherein said poly-(alkenyl aromatic) is substantially devoid of mineral oil.
CNA2006800408917A 2005-11-02 2006-10-26 Poly(arylene ether) blend and method of making same Pending CN101300303A (en)

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